Foundry mix including resorcinol

ABSTRACT

A foundry mix includes a major amount of a foundry aggregate and an effective binding amount of a binder system. The binder system cures in the presence of sulfur dioxide and a free radical initiator. The binder system may include (1) 10 to 70 parts by weight of an epoxy novolac resin; (2) 0.5 to 10 parts by weight of resorcinol; (3) 20 to 70 parts by weight of a monomeric or polymeric acrylate; and (4) an effective amount of a free radical initiator. Notably, (1), (2), (3) and (4) are separate components or mixed with another of said components, provided (4) is not mixed with (3), where said parts by weight are based upon 100 parts of the binder system.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. patent Ser. No.15/875,554 filed on Jan. 19, 2018 and claims the benefit of U.S.Provisional Application Ser. No. 62/449,157, filed on Jan. 23, 2017; thedisclosure of which is incorporated herein by reference.

BACKGROUND Technical Field

The present disclosure relates generally to foundry binder systems,which will cure in the presence of sulfur dioxide and a free radicalinitiator, comprising (a) an epoxy novolac resin; (b) preferably abisphenol F epoxy resin alone or bisphenol F epoxy resin with a slightamount of bisphenol A epoxy resin; (c) an acrylate; (d) resorcinol orother polyhydroxy benzenes; and (e) an effective amount of a freeradical initiator. The foundry binder systems are used for makingfoundry mixes. The foundry mixes are used to make foundry shapes (suchas cores and molds) which are used to make metal castings.

Background Information

Foundry binder systems, which cure in the presence of a free radicalinitiator, are known in the art. For instance, U.S. Pat. Nos. 6,604,567;6,662,854; 6,684,936; 6,686,402; and 7,723,401 disclose foundry coremold systems that include an epoxy resins that cure in the presence of afree radical initiator.

In order for the epoxy resins to be useful in these situations, theepoxy resin must be used in conjunction with an acrylic monomer orpolymer, typically trimethylolpropane triacrylate (TMPTA) however otheracrylates are entirely possible.

Typically, these binders are packaged in two parts. One part (“PartOne”) is a mixture of a resins (such as bisphenol A epoxy resin orbisphenol-F epoxy resin) and cumene hydroperoxide (the free radicalinitiator). The other part (“Part Two”) is a mixture of one or moreresins, a multifunctional acrylate, and other optional components. Themultifunctional acrylate is typically trimethylolpropane triacrylate(TMPTA).

Part One and Part Two of the binder are mixed with a foundry aggregate,typically sand, to form a foundry mix. The total amount of binder usedto form the foundry mix. The foundry mix may be blown or compacted intoa pattern where it is gassed with sulfur dioxide (SO2) to produce acured core or mold. Thereafter, molten metal is poured into the curedcore/mold and allowed to form a desired shape, such as an engine block,amongst many other shapes.

SUMMARY

While these prior art foundry binder systems (i.e., U.S. Pat. Nos.6,604,567; 6,662,854; 6,684,936; 6,686,402; and 7,723,401) may bebeneficial for specific applications, they are not without drawbacks.For example, a need continues to exist for foundry binder systems thatutilize more acrylate, which could lead to additional benefits.Moreover, the inventors have determined that the “other optionalcomponents” may significantly affect the performance of the foundrybinder systems. The present disclosure addresses these and other issue.The present disclosure addresses these issues by providing a foundry mixthat includes resorcinol which has, upon information and belief,heretofore never been utilized in foundry mixes.

In one particular embodiment of the present disclosure, a foundry bindersystem may provide 20 to 70 weight percent of epoxy novolac resin,preferably from 35 to 60 weight percent; 10 to 25 weight percent of freeradical initiator, preferably from 15 to 20 weight percent; and 20 to 35weight percent of multifunctional acrylate, preferably from 25 to 32weight percent, where the weight percent is based upon 100 parts of thebinder system.

In one particular example, an embodiment of the present disclosure mayprovide a foundry binder system utilizing sand, a Part One mix, and aPart Two mix of the foundry binder system. Part One includes Bisphenol Fepoxy resin at 70% (parts by weight) and cumene hydroperoxide (TRIGONOXK-90) at 30% (parts by weight). Part Two includes epoxy novolac resin at31% (parts by weight), resorcinol at 3.8% (parts by weight), dibasicester at 7.6% (parts by weight), an acrylate at 56.40% (parts byweight), and silane at 1.2% (parts by weight).

In another particular example, an embodiment of the present disclosuremay provide a foundry binder system utilizing sand, Part One, and PartTwo of the foundry binder system. Part One includes Bisphenol F epoxyresin at 69% (parts by weight), Bisphenol A epoxy resin at 1% (parts byweight), and cumene hydroperoxide (TRIGONOX K-90) at 30% (parts byweight). Part Two includes epoxy novolac resin at 31% (parts by weight),resorcinol at 3.8% (parts by weight), dibasic ester at 7.6% (parts byweight), an acrylate at 56.40% (parts by weight), silane at 1.2% (partsby weight).

In another particular example, an embodiment of the present disclosuremay provide a foundry binder system utilizing sand, Part One, and PartTwo of the foundry binder system. Part One includes Bisphenol F epoxyresin at 68% (parts by weight), Bisphenol A epoxy resin at 2% (parts byweight), and cumene hydroperoxide (TRIGONOX K-90) at 30% (parts byweight). Part Two includes epoxy novolac resin at 31% (parts by weight),resorcinol at 3.8% (parts by weight), dibasic ester at 7.6% (parts byweight), an acrylate at 56.40% (parts by weight), silane at 1.2% (partsby weight).

In another particular example, an embodiment of the present disclosuremay provide a method for preparing a foundry shape comprising: (a)introducing a foundry mix into a pattern to form a foundry shape; and(b) curing said shape with gaseous sulfur dioxide; wherein said foundrymix comprises: (c) 70 to 99 parts by weight of a foundry aggregate, anda foundry binder comprising: (d) 20 to 70 parts by weight of an epoxynovolac resin; (e) 20 to 35 parts by weight of a multifunctionalacrylate; (f) 0.5 to 10 parts by weight of resorcinol; (g) 10 to 25parts by weight of amount of a free radical initiator, provided (d) isnot mixed with (g), and where said parts by weight are based upon 100parts of binder.

In another particular example, an embodiment of the present disclosuremay provide a foundry binder system including: an aggregate; a firstportion (Part One), wherein Part One includes an epoxy resin in a rangefrom 25 to 70 parts by weight, and cumene hydroperoxide in a range from10 to 40 parts by weight; a second portion (Part Two), wherein Part Twoincludes an epoxy novolac resin in a range from 10 to 40 parts byweight, resorcinol in a range from 0.5 to 10 parts by weight, dibasicester in a range from 2 to 10 parts by weight, an acrylate in a rangefrom 20 to 70 parts by weight, and silane in a range from 0.2 to 5 partsby weight; and wherein the aggregate, Part One, and Part Two are mixedtogether and exposed to sulfur dioxide to cure the aggregate into afoundry mold.

In yet another aspect, one exemplary embodiment of the presentdisclosure may provide a process for preparing a foundry shapecomprising: introducing a foundry mix into a pattern to form a foundryshape; and curing said shape with gaseous sulfur dioxide; wherein saidfoundry mix comprises: (a) from 70 to 99 parts by weight of a foundryaggregate, and a foundry binder comprising: (b) 20 to 70 parts by weightof an epoxy novolac resin; (c) 20 to 35 parts by weight of amultifunctional acrylate; (d) 0.5 to 10 parts by weight of resorcinol;(e) an effective amount of amount of a free radical initiator, provided(b) is not mixed with (e), and where said parts by weight are based upon100 parts of binder.

In yet another aspect, one exemplary embodiment of the presentdisclosure may provide a method of casting a metal article comprising:fabricating a foundry shape by introducing a foundry mix into a patternto form the foundry shape, and curing said shape with gaseous sulfurdioxide; wherein said foundry mix comprises: (a) from 70 to 99 parts byweight of a foundry aggregate, and a foundry binder comprising: (b) 20to 70 parts by weight of an epoxy novolac resin; (c) 20 to 35 parts byweight of a multifunctional acrylate; (d) 0.5 to 10 parts by weight ofresorcinol; (e) an effective of amount of a free radical initiator,provided (b) is not mixed with (e), and where said parts by weight arebased upon 100 parts of binder; pouring said metal while in the liquidstate into said foundry shape; allowing said metal to cool and solidify;and separating the cast article.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

A sample embodiment of the disclosure is set forth in the followingdescription, is shown in the drawings and is particularly and distinctlypointed out and set forth in the appended claims. The accompanyingdrawings, which are fully incorporated herein and constitute a part ofthe specification, illustrate various examples, methods, and otherexample embodiments of various aspects of the disclosure. It will beappreciated that the illustrated element boundaries (e.g., boxes, groupsof boxes, or other shapes) in the figures represent one example of theboundaries. One of ordinary skill in the art will appreciate that insome examples one element may be designed as multiple elements or thatmultiple elements may be designed as one element. In some examples, anelement shown as an internal component of another element may beimplemented as an external component and vice versa. Furthermore,elements may not be drawn to scale.

FIG. 1 is a diagram representing a foundry binder system including anaggregate, a first portion (Part One), and a second portion (Part Two),wherein the aggregate, Part One, and Part Two are mixed together andexposed to sulfur dioxide to cure the aggregate into a foundry mold.

FIG. 2 is a flowchart representing an exemplary method of casting ametal article.

FIG. 3 is a flowchart representing an exemplary method of preparing afoundry shape.

Similar numbers refer to similar parts throughout the drawings.

DETAILED DESCRIPTION

The present disclosure provides a system that provides specific utilityfor sandcasting molds that are used are used for forming molten metal.As depicted in FIG. 1, the chemical system 100 includes a first portion(i.e., Part One) 102 and a second portion (i.e., Part Two) 104 that arestored separately and then mixed together with foundry aggregate 106(i.e., sand). Collectively, the chemical system 100 includes a majoramount of a foundry aggregate 106, an effective binding amount of abinder system, which will cure in the presence of sulfur dioxide and afree radical initiator, comprising 20 to 40 parts by weight of an epoxynovolac resin; 40 to 60 parts by weight of a monomeric or polymericacrylate; 1 to 5 parts by weight of resorcinol, and an effective amountof a free radical initiator.

Bisphenol F epoxy resin, and possibly a small amount of Bisphenol Aepoxy resin, and cumene hydroperoxide (the free radical initiator)collectively define Part One 102 and are first stored independently inthe first portion. Epoxy novolac resin, resorcinol, a dibasic ester, andan acrylate, and in one particular embodiment, collectively define PartTwo 104 and are stored independently in the second portion. Then, thefirst and second portions are mixed with the foundry aggregate andexposed to sulfur dioxide which effects curing of the chemical system toform a foundry mold. Notably, Part Two 104 may include additionalsubstances, or may have fewer substances, however in accordance with thepresent disclosure, Part Two 104 ordinarily includes resorcinol.

The following description provides more information on the abovereferenced portions of Part One 102 of the foundry binder system andPart Two 104 of the foundry binder system 100 in accordance with thepresent disclosure.

Part One of the Foundry Binder System

Part One 102 of the system 100 may use of epoxy novolacs as the SO2cured binder, instead of epoxy resins based on bisphenol A epoxy resinor bisphenol F epoxy resin alone. In one particular embodiment, this mayimprove the hot strength of cores and molds made with the binder, sothat the cores and molds hold up better during microwave andconventional oven drying operations. The magnitude of the improvement inperformance, as measured by tensile strength is identified hereinafter.Cores and molds made from the binders described in this invention aremuch more rigid at typical oven curing temperatures and resistdistortion and cracking. Furthermore, the cores can be handled soonerbecause the cool-down time required is not as long, which increasesproductivity.

While the epoxy resin of Part One 102 is Bisphenol F epoxy resin (withthe possibility of a small amount of Bisphenol A epoxy resin, such as 1part by weight or 2 parts by weight or 3 parts by weight), another epoxyresin is entirely possible, such that the resin have one or more epoxidegroups, i.e.,

wherein x is zero or a whole number, typically from 1 to 4. Otherpotential epoxy resins typically used in foundry applications arediglycidyl ethers of bisphenol A, which is a monomer. These are made byreacting epichlorohydrin with the monomer bisphenol A in the presence ofan alkaline catalyst. By controlling the operating conditions andvarying the ratio of epichlorohydrin to bisphenol A, products ofdifferent molecular weight can be made. Other commonly used epoxy resinsinclude the diglycidyl ethers of other bisphenol compounds such asbisphenol B, F, G and H, each of which are monomers. Epoxy resins of thetype described above based on various bisphenols are available from awide variety of commercial sources. Monomers such as bisphenol F have achemical composition generally depicted as follows:

Epoxy resins such as bisphenol F epoxy resin have a different chemicalcomposition than monomer compounds. Specifically, bisphenol F epoxyresin has a chemical composition generally depicted as follows:

The epoxy novolac resin component of the present disclosure, however,comprises an “epoxy novolac resin”. Epoxy novolac resins are lesscommonly known and used than other epoxy resins. Epoxy novolac resinsare typically prepared by reacting an epihalohydrin, e.g.epichlorohydrin, with the resinous condensate of an aldehyde, e.g.formaldehyde, and either a monohydric phenol, e.g. phenol itself, or apolyhydric phenol, preferably in the presence of a basic catalyst, e.g.sodium or potassium hydroxide, by methods well known in the art.Examples of epoxy novolac resins include epoxy cresol and epoxy phenolnovolacs, which are produced by reacting a novolac resin (usually formedby the reaction of orthocresol or phenol and formaldehyde) withepichlorohydrin, 4-chloro-1,2-epoxybutane, 5-bromo-1,2-epoxypentane,6-chloro-1,3-epoxyhexane and the like.

The epoxy novolac resin, or blends of epoxy novolac resins, used in thebinders, typically have an average epoxide functionality of at least 2.2to 3.5, preferably from about 2.3 to about 3.0. Particularly preferredare epoxy novolacs having an average weight per epoxy group of 165 to200. Although the viscosities of the epoxy novolac resins are high,usually greater than 5,000 cps at 25° C., the epoxy component viscosityis reduced to a workable level when the epoxy novolac resin is mixedwith the free radical initiator and/or solvent.

The foundry binder system 100 of the present disclosure preferablycontains some bisphenol F epoxy resin in an amount (typically from 60 to80 parts by weight based on 100 parts of binder, and in one particularexample about 70 parts by weight), which is useful in reducing theviscosity of the epoxy novolac resin, but does not significantly affectthe other required properties of the binders or cores made with thebinder. The binder preferably contains sufficient bisphenol F epoxyresin to obtain a binder (or the parts of the binder if the binder isformulated as more than one part), with a viscosity less than 2000centipoise at room temperature, preferably less than 1500 centipoise,and most preferably less than 900 centipoise.

Although not necessarily preferred, other epoxy resins, such asbisphenol A epoxy resin, may also be added to the binder to lower thecosts of the binder. In one exemplary embodiment, not more than 10 partsby weight (i.e., weight percent) of these other epoxy resins andmonomeric bisphenol A are typically used, where the weight percent isbased upon the weight percent of the epoxy novolac resin in the bindersystem. Other epoxy resins, such as bisphenol A epoxy resin andbisphenol F epoxy resin, and monomeric bisphenol compounds, such asbisphenol A, may be added to the binder.

Examples of other epoxy resins include halogen-substituted aliphaticepoxides and diglycidyl ethers of other bisphenol compounds such asbisphenol B, F, G, and H epoxy resins. Examples of halogen-substitutedaliphatic epoxides include epichlorohydrin, 4-chloro-1,2-epoxybutane,5-bromo-1,2-epoxypentane, 6-chloro-1,3-epoxyhexane and the like. Themost widely used epoxy resins are diglycidyl ethers of bisphenol A.

The free radical initiator is a peroxide and/or hydroperoxide. Examplesinclude ketone peroxides, peroxy ester free radical initiators, alkyloxides, chlorates, perchlorates, and perbenzoates, Preferably, however,the free radical initiator is a hydroperoxide or a mixture of peroxideand hydroperoxide. Hydroperoxides particularly preferred in theinvention include t-butyl hydroperoxide, cumene hydroperoxide,paramenthane hydroperoxide, etc. The organic peroxides may be aromaticor alkyl peroxides. Examples of useful diacyl peroxides include benzoylperoxide, lauroyl peroxide and decanoyl peroxide. Examples of alkylperoxides include dicumyl peroxide and di-t-butyl peroxide.

Cumene hydroperoxide and/or a multifunctional acrylate, such astrimethylolpropane triacrylate, may added to the epoxy novolac resinbefore mixing it with the foundry aggregate. Optionally, a solvent orsolvents may be added to reduce system viscosity or impart otherproperties to the binder system such as humidity resistance. Examples ofsolvents include aromatic hydrocarbon solvents, such as such aso-cresol, benzene, toluene, xylene, ethylbenzene, and naphthalenes;reactive epoxide diluents, such as glycidyl ether; or an ester solvent,such as dioctyl adipate, rapeseed methyl ester, and the like, ormixtures thereof. If a solvent is used, sufficient solvent should beused so that the resulting viscosity of the epoxy resin component isless than 1,000 centipoise, preferably less than 400 centipoise.Generally, however, the total amount of solvent is used in an amount of0 to 25 weight percent based upon the total weight of the epoxy resin.

Part Two of the Foundry Binder System

Part Two 104 of the foundry binder system includes the reactiveunsaturated acrylic monomer, polymer, or mixture thereof containsethylenically unsaturated bonds. Examples of such materials include amultifunctional acrylate, such as trimethylolpropane triacrylate (TMPTA)or any other variety of monofunctional, difunctional, trifunctional,tetrafunctional and pentafunctional monomeric acrylates andmethacrylates. A representative listing of these monomers includes alkylacrylates, acrylated epoxy resins, cyanoalkyl acrylates, alkylmethacrylates, cyanoalkyl methacrylates, and difunctional monomericacrylates. Other acrylates, which can be used, includetrimethylolpropane triacrylate, methacrylic acid and 2-ethylhexylmethacrylate. Typical reactive unsaturated acrylic polymers, which mayalso be used include epoxy acrylate reaction products,polyester/urethane/acrylate reaction products, acrylated urethaneoligomers, polyether acrylates, polyester acrylates, and acrylated epoxyresins.

Part Two 104 of the foundry binder system 100 of the present disclosurefurther includes a phenolic substance, such as a polyhydroxy benzene,preferably a di-hydroxy and tri-hydroxy benzene, still more preferablyresorcinol (1,3-dihydroxy benzene). Some other exemplary non-limitingsuitable examples of the resorcinol compound include non-functionalizedresorcinol compounds such as resorcinol; and functionalized resorcinolcompounds such as orcinol, 2-methylresorcinol, phloroglucinol,1,2,4-benzenetriol, pyrogallol, 3,5-dihydroxybenzaldehyde,2,4-dihydroxybenzaldehyde, 4-ethylresorcinol, 2,5-dimethylresorcinol,5-methylbenzene-1,2,3-triol, 3,5-dihydroxybenzyl alcohol,2,4,6-trihydroxytoluene, 4-chlororesorcinol,2′,6′-dihydroxyacetophenone, 2′,4′-dihydroxyacetophenone,3′,5′-dihydroxyacetophenone, 2,4,5-trihydroxybenzaldehyde,2,3,4-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde,3,5-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid,2,6-dihydroxybenzoic acid, 1,3-dihydroxynaphthalene,2′,4′-dihydroxypropiophenone, 2′,4′-dihydroxy-6′-methylacetophenone,1-(2,6-dihydroxy-3-methylphenyl)ethanone, 3-methyl3,5-dihydroxybenzoate, methyl 2,4-dihydroxybenzoate, gallacetophenone,2,4-dihydroxy-3-methylbenzoic acid, 2,6-dihydroxy-4-methylbenzoic acid,methyl 2,6-dihydroxybenzoate, 2-methyl-4-nitroresorcinol,2,4,5-trihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid,2,3,4-trihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid,2-nitrophioroglucinol or a combination thereof. In some embodiments, theresorcinol compound is resorcinol, orcinol, 2-methylresorcinol,phloroglucinol, 1,2,4-benzenetriol, pyrogallol,3,5-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 4-ethylresorcinol,4-chiororesorcinol or a combination thereof.

In accordance with a non-limiting example of the present disclosure, theuse of the polyhydroxy benzene, preferably a di-hydroxy and tri-hydroxybenzene, still more preferably resorcinol (1,3-dihydroxy benzene) inPart Two 104 of system 100 provides some advantages to the binder. Forexample, some advantages of the polyhydroxy benzene enable the resin tohave a higher thermal stability (improves hot-strength); enables theresin to establish an increase in front-end tensile strength (earlytensile strength is higher for improved handling of cores); and thehumidity resistance is improved.

Part Two 104 of the foundry binder system 100 further includes A-187silane, or another epoxy functional silanes which may be suitable foruse as adhesion promoters in, urethane, epoxy, polysulfide, silicone,and acrylic caulks, coatings, sealants and adhesives. The silane mayprovide enhanced electrical properties of epoxy based electronicencapsulant and packaging materials, resulting from improved bondingbetween resin and substrate or filler. The silane provides itself usefulfor the quartz (in the sand aggregate) filled epoxy encapsulants,pre-mix formulations, sand-filled epoxy concrete patching materials, andmetal filled epoxy materials suitable for mold die tools. Some exemplarysilanes aside from A187 silane include but are not limited to mixturesof methyltrimethoxysilane and propyltrimethoxysilane, ofpropyltrimethoxysilane and vinyltrimethoxysilane orphenyltrimethoxysilane and propyltrimethoxysilane, and ofphenyltriethoxysilane and propyltriethoxysilane, to name but a fewexamples. Other useful silanes may include aminoalkyl-functionalalkoxysilane which carries in particular an aminoalkyl group from theseries consisting of aminoethylaminopropyl,aminoethylaminoethylaminopropyl, N-methylaminopropyl,N-(n-butyl)aminopropyl, N-cyclohexylaminopropyl, andN-phenylaminopropyl, and at least one alkoxy group from the seriesconsisting of methoxy, ethoxy, and propoxy. Examples of such are3-aminopropyltrialkoxysilanes, such as 3-aminopropyltrimethoxysilane,3-aminopropyltriethoxysilane,N-aminoethyl-3-aminopropyltrialkoxysilanes,N-aminoethyl-N-aminoethyl-3-aminopropyltrialkoxysilanes,N-methyl-aminopropyltrialkoxysilanes,N-n-butyl-aminopropyltrialkoxysilanes,N-cyclohexyl-aminopropyltrialkoxysilanes,N-phenyl-aminopropyltrialkoxysilanes,3-aminopropyl-methyldialkoxysilanes,N-aminoethyl-3-aminopropyl-methyldialkoxysilanes,N-aminoethyl-N-aminoethyl-3-aminopropyl-methyldialkoxysilanes,N-methyl-aminopropyl-methyldialkoxysilanes,N-n-butyl-aminopropyl-methyldialkoxysilanes,N-cyclohexyl-aminopropyl-methyldialkoxysilanes, andN-phenyl-aminopropyl-methyl.

It will be apparent to those skilled in the art that other additivessuch as other silanes, silicones, benchlife extenders, release agents,defoamers, wetting agents, etc. can be added to the aggregate, orfoundry mix. The particular additives chosen will depend upon thespecific purposes of the formulator.

Mixing Part One and Part Two with Aggregate

Various types of aggregates 106 and amounts of binder are used toprepare foundry mixes by methods well known in the art. Ordinary shapes,shapes for precision casting, and refractory shapes can be prepared byusing the binder systems and proper aggregate. The amount of binder andthe type of aggregate used are known to those skilled in the art. Thepreferred aggregate 106 employed for preparing foundry mixes is sandwherein at least about 70 weight percent, and preferably at least about85 weight percent, of the sand is silica. Other suitable aggregatematerials for ordinary foundry shapes include zircon, olivine,aluminosilicate, chromite sands, and the like.

In ordinary sand type foundry applications, the amount of binder isgenerally no greater than about 10% by weight and frequently within therange of about 0.5% to about 7% by weight based upon the weight of theaggregate. Most often, the binder content for ordinary sand foundryshapes ranges from about 0.6% to about 5% by weight based upon theweight of the aggregate in ordinary sand-type foundry shapes.

The foundry mix is molded into the desired shape by ramming, blowing, orother known foundry core and mold making methods. The shape is thencured almost instantaneously by the cold-box process, using vaporoussulfur dioxide as the curing agent (most typically a blend of nitrogen,as a carrier, and sulfur dioxide containing from 35 weight percent to 65weight percent sulfur dioxide), described in U.S. Pat. Nos. 4,526,219and 4,518,723, amongst others, which are hereby incorporated byreference. The shaped article is preferably exposed to effectivecatalytic amounts of 100 percent vaporous sulfur dioxide, although minoramounts of a carrier gas may also be used. The exposure time of the sandmix to the gas is typically from 0.5 to 3 seconds. Although the foundryshape is cured after gassing with sulfur dioxide, oven drying may berequired if the foundry shape is coated with a water based refractorycoating.

Typically, the amounts of the components used in the binder system arefrom 20 to 70 weight percent of epoxy novolac resin, preferably from 35to 60 weight percent; 10 to 25 weight percent of free radical initiator,preferably from 15 to 20 weight percent; and 20 to 35 weight percent ofmultifunctional acrylate, preferably from 25 to 32 weight percent, wherethe weight percent is based upon 100 parts of the binder system.

The core and/or mold may be formed into an assembly. When makingcastings, the assembly is typically coated with a water-based refractorycoating and passed through a conventional or microwave oven to removethe water from the coating. The item is then ready to be handled forfurther processing. In one particular embodiment, the process forpreparing a foundry shape includes introducing a foundry mix into apattern to form a foundry shape; and curing said shape with gaseoussulfur dioxide.

In accordance with one aspect of the present disclosure, the shape curedcore is formed into the shape of a negative engine block. This allowsmolten metal, such as Aluminum, or an aluminum-based alloy, to be pouredinto the mold. The metal is allowed to cool and cure so as to form anengine block or other desired shaped.

In operation, a method of casting a metal article may includefabricating a foundry shape by introducing a foundry mix into a patternto form the foundry shape, and curing said shape with gaseous sulfurdioxide; pouring said metal while in the liquid state into said foundryshape, which could be shaped as a negative engine block; allowing saidmetal to cool and solidify; and then separating the cast article, suchas the engine block. In some instances, the cast article (i.e., theengine block) can be shaken to release the foundry aggregate from thecooled, cured, and cast metal article.

FIG. 2 depicts an exemplary method of casting a metal article generallyat 200. The method 200 may include fabricating a foundry shape byintroducing a foundry mix into a pattern to form the foundry shape, andcuring said shape with gaseous sulfur dioxide, which is shown generallyat 202. In one non-limiting example, the foundry mix includes: (a) 20 to70 parts by weight of an epoxy novolac resin; (b) 20 to 65 parts byweight of a multifunctional acrylate; (c) 0.5 to 10 parts by weight ofresorcinol; (d) an effective of amount of a free radical initiator,provided (a) is not mixed with (d) prior to mixing the foundry mix, andwhere said parts by weight are based upon 100 parts of the foundry mix.The method 200 may further include pouring said metal while in theliquid state into said foundry shape, which is shown generally at 204.The method 200 may further include allowing said metal to cool andsolidify, which is shown generally at 206. The method 200 may furtherinclude separating the cast article, which is shown generally at 208. Inone example, method 200 may further provide wherein the foundry mixincludes at least 1 parts by weight of bisphenol A epoxy resin. In thisor another example, method 200 may further provide wherein the foundrymix further includes (e) a dibasic ester in a range from 2 to 10 partsby weight. In this or another example, method 200 may further providewherein the binder system further includes (6) a silane in a range from0.5 to 2 parts by weight. In this or another example, method 200 mayfurther provide wherein the resorcinol is about 3.8 parts by weight.

FIG. 3 depicts an exemplary method or process for preparing a foundryshape generally at 300. Method 300 may include introducing a foundry mixinto a pattern to form a foundry shape, which is shown generally at 302.Method 300 may include curing said shape with gaseous sulfur dioxide,which is shown generally at 304. In one particular embodiment of method300 said foundry mix comprises: (a) from 70 to 99 parts by weight of afoundry aggregate, and a foundry binder comprising: (b) 20 to 70 partsby weight of an epoxy novolac resin; (c) 20 to 35 parts by weight of amultifunctional acrylate; (d) 0.5 to 10 parts by weight of resorcinol,however other parts by weight are possible, such as 3.8 parts by weight;(e) an effective amount of a free radical initiator, provided (b) is notmixed with (e), and where said parts by weight are based upon 100 partsof binder.

Example Tensile Tests

The numbered examples are examples that illustrate the practice of thepresent disclosure. All parts are by weight, unless otherwise indicated.

The tensile strength of “dog bones” formed from the Part One 102 andPart Two 104 portions of the present disclosure is used to determinedifferences in tensile strength when subjected to a tensile force. Thetensile tester used in each of the following examples consists of a dogbone-shaped samples formed from the Part One 102 and Part Two 104portions of the present disclosure and cured in the presence of SO2. Thetensile tester is a Thwing-Albert QC-3A.

Dog Bone Preparation for Tensile Strength Test Procedure

In a Hobart mixing bowl N-50 (Serial No. 31-1402-254) using speed 1 withstainless steel paddle, 4000 grams of standard sand at 72° F. are mixedwith 1.20% of the binder (epoxy resin and additives pre-blended with theTMPTA) based on sand. Example 1 utilizes Badger FW-55 sand and Example 2utilizes Wedron 430 sand. The Part One/Part Two ratio is 50:50 (i.e.,1:1). Part One mass is 24 grams and Part Two mass is 24 grams. Thismixture is mixed at speed #1 for two minutes. After two minutes, sandmix is flipped several times to blend any dry sand at the bottom of thebowl into the sand-binder mix. Then the mixture is mixed for another twominutes, for a total of 4 minutes.

The sand-binder mix is placed in a “dog bone” form, where it is gassedfor 12 seconds with 100% anhydrous SO2 (at 30 PSI) and after a 3 seconddwell time, the dog bone is purged with N2 for thirty seconds (at 35PSI). The SO2 gas line temperature is 225° F. and the N2 gas linetemperature is 225° F.

After purging the dog bone, the dog bone is connected to a tensilestrength tester. The tensile tester is a Thwing-Albert QC-3A (Serial No.62229). The tensile strength conditions provide the tensile testermoving at a speed of 2 inch/min until contacting the dog bone, then oncecontact is established the speed drops to 0.2 inch/min.

Part One and Part Two are mixed with the sand and cured into a dog bonein the method described above and tested by the tensile tester. Thetensile strength tester tested the dog bone tensile strength atdifferent time intervals after curing. The first time interval was after2 minutes from curing (at about 30% relative humidity (RH)), the secondtime interval was 2 hours from curing (at about 30% RH), the third timeinterval was 24 hours from curing (at 30% RH), and the fourth timeinterval was 24 hours from curing (at about 75% RH). Each ambienttemperature was about 73° F. For each time interval, three tensilestrength results were obtained (in psi) and averaged.

Example One

Example One utilizes sand (Badger FW-55), Part One, and Part Two of thefoundry binder system. Part One includes Bisphenol F epoxy resin (DER354; lot D344F4G036) at 70% (parts by weight) and cumene hydroperoxide(TRIGONOX K-90) at 30% (parts by weight). Part Two includes epoxynovolac resin (DEN 431; lot D344F79940) at 31% (parts by weight),resorcinol at 3.8% (parts by weight), dibasic ester (DBE) at 7.6%, anacrylate (SR 352H TMPTA) at 56.40% (parts by weight), silane (A187) at1.2%.

After two minutes from curing at about 30% RH, the three tensilestrength test results of the Example One dog bone sample were 217.0,194.3, and 187.8, for an average of 199.7 psi. After two hours fromcuring at about 30% RH, the three tensile strength test results were251.8, 237.5, and 225.9, for an average of 238.4 psi. After 24 hoursfrom curing at about 30% RH, the three tensile strength test resultswere 248.6, 270.1, and 274.6, for an average of 264.4 psi. After 24hours from curing at about 75% RH, the three tensile strength testresults were 138.2, 137.6, and 128.6, for an average of 134.8 psi.

Example Two

Example Two utilizes sand (Badger FW-55), Part One, and Part Two of thefoundry binder system. Part One includes Bisphenol F epoxy resin (DER354; lot D344F4G036) at 70% (parts by weight) and cumene hydroperoxide(TRIGONOX K-90) at 30% (parts by weight). Part Two includes epoxynovolac resin (DEN 431; lot D344F79940) at 31% (parts by weight),resorcinol at 3.8% (parts by weight), dibasic ester (DBE) at 7.6%, anacrylate (SR 295 acrylic) at 56.40% (parts by weight), silane (A187) at1.2%.

After two minutes from curing at about 30% RH, the three tensilestrength test results of the Example Two dog bone sample were 220.1,203.4, and 189.6, for an average of 204.4 psi. After two hours fromcuring at about 30% RH, the three tensile strength test results were250.0, 242.1, and 241.7, for an average of 244.6 psi. After 24 hoursfrom curing at about 30% RH, the three tensile strength test resultswere 270.3, 264.9, and 267.0, for an average of 267.4 psi. After 24hours from curing at about 75% RH, the three tensile strength testresults were 155.3, 172.4, and 159.6, for an average of 162.4 psi.

Example Three

Example Three utilizes sand (Wedron 430), Part One, and Part Two of thefoundry binder system. Part One includes Bisphenol F epoxy resin (DER354; lot D344F4G036) at 70% (parts by weight) and cumene hydroperoxide(TRIGONOX K-90) at 30% (parts by weight). Part Two includes epoxynovolac resin (DEN 431; lot D344F79940) at 31% (parts by weight),resorcinol at 3.8% (parts by weight), dibasic ester (DBE) at 7.6%, anacrylate (SR 351H TMPTA) at 56.40% (parts by weight), silane (A187) at1.2%.

After two minutes from curing at about 30% RH, the three tensilestrength test results of the Example Three dog bone sample were 197.3,164.5, and 144.1, for an average of 168.6 psi. After two hours fromcuring at about 30% RH, the three tensile strength test results were231.4, 216.8, and 199.6, for an average of 215.9 psi. After 24 hoursfrom curing at about 30% RH, the three tensile strength test resultswere 252.7, 231.1, and 249.3, for an average of 244.4 psi. After 24hours from curing at about 75% RH, the three tensile strength testresults were 131.0, 123.0, and 105.2, for an average of 119.7 psi.

Example Four

Example Four utilizes sand (Wedron 430), Part One, and Part Two of thefoundry binder system. Part One includes Bisphenol F epoxy resin (DER354; lot D344F4G036) at 70% (parts by weight) and cumene hydroperoxide(TRIGONOX K-90) at 30% (parts by weight). Part Two includes epoxynovolac resin (DEN 431; lot D344F79940) at 31% (parts by weight),resorcinol at 3.8% (parts by weight), dibasic ester (DBE) at 7.6%, anacrylate (SR 351H TMPTA) at 56.40% (parts by weight), silane (A187) at1.2%.

After two minutes from curing at about 30% RH, the three tensilestrength test results of the Example Four dog bone sample were 179.5,157.1, and 150.3, for an average of 162.3 psi. After two hours fromcuring at about 30% RH, the three tensile strength test results were202.4, 219.6, and 212.1, for an average of 211.4 psi. After 24 hoursfrom curing at about 30% RH, the three tensile strength test resultswere 201.4, 236.2, and 231.6, for an average of 223.1 psi. After 24hours from curing at about 75% RH, the three tensile strength testresults were 137.8, 138.1, and 111.8, for an average of 129.2 psi.

Example Five

Example Five utilizes sand (Wedron 520), Part One, and Part Two of thefoundry binder system. Part One includes Bisphenol F epoxy resin (DowDER 354) at 70% (parts by weight) and cumene hydroperoxide (TRIGONOXK-90) at 30% (parts by weight). Part Two includes epoxy novolac resin(DEN 431; lot D344F79940) at 31% (parts by weight), resorcinol at 3.8%(parts by weight), dibasic ester (DBE) at 7.6%, an acrylate (SR 351HTMPTA) at 56.40% (parts by weight), silane (A187) at 1.2%.

After two minutes from curing at about 31% RH, the three tensilestrength test results of the Example Five dog bone sample were 213.2,224.3, and 215.9, for an average of 217.8 psi. After two hours fromcuring at about 31% RH, the three tensile strength test results were249.8, 228.7, and 248.3, for an average of 242.3 psi. After 24 hoursfrom curing at about 31% RH, the three tensile strength test resultswere 276.7, 260.4, and 237.4, for an average of 258.2 psi. After 24hours from curing at about 75% RH, the three tensile strength testresults were 125.5, 124.6, and 120.8, for an average of 123.6 psi.

Example Six

Example Six utilizes sand (Wedron 520), Part One, and Part Two of thefoundry binder system. Part One includes Bisphenol F epoxy resin (DowDER 354) at 70% (parts by weight) and cumene hydroperoxide (TRIGONOXK-90) at 30% (parts by weight). Part Two (a proprietary mix) includesepoxy novolac resin (Dow DEN 431) at 33.85% (parts by weight),resorcinol at 1.9% (parts by weight), dibasic ester (DBE) at 3.8%, anacrylate (SR 351H TMPTA) at 59.25% (parts by weight), silane (A187) at1.2%.

After two minutes from curing at about 31% RH, the three tensilestrength test results of the Example Six dog bone sample were 169.6,176.6, and 171.6, for an average of 172.6 psi. After two hours fromcuring at about 31% RH, the three tensile strength test results were226.6, 225.9, and 208.7, for an average of 220.4 psi. After 24 hoursfrom curing at about 31% RH, the three tensile strength test resultswere 226.7, 241.9, and 259.7, for an average of 242.8 psi. After 24hours from curing at about 75% RH, the three tensile strength testresults were 113.5, 109.0, and 105.2, for an average of 109.2 psi.

Example Seven

Example Seven utilizes sand (Wedron 520), Part One, and Part Two of thefoundry binder system. Part One includes Bisphenol F epoxy resin (DowDER 354) at 70% (parts by weight) and cumene hydroperoxide (TRIGONOXK-90) at 30% (parts by weight). Part Two (a proprietary mix) includesepoxy novolac resin (Dow DEN 431) at 36.7% (parts by weight), anacrylate (SR 351H TMPTA) at 62.1% (parts by weight), silane (A187) at1.2%.

After two minutes from curing at about 31% RH, the three tensilestrength test results of the Example Seven dog bone sample were 155.9,178.6, and 173.9, for an average of 169.5 psi. After two hours fromcuring at about 31% RH, the three tensile strength test results were210.4, 221.0, and 221.9, for an average of 217.8 psi. After 24 hoursfrom curing at about 31% RH, the three tensile strength test resultswere 234.2, 213.9, and 205.1, for an average of 217.7 psi. After 24hours from curing at about 75% RH, the three tensile strength testresults were 112.8, 109.7, and 91.6, for an average of 104.7 psi.

Example Eight

Example Eight utilizes sand (Wedron 520), Part One, and Part Two of thefoundry binder system. Part One (a proprietary mix) includes Bisphenol Fepoxy resin (DER 354) at 69% (parts by weight), Bisphenol A epoxy resin(Dow DER 383) at 1% (parts by weight), and cumene hydroperoxide(TRIGONOX K-90) at 30% (parts by weight). Part Two includes epoxynovolac resin (Dow DEN 431) at 31% (parts by weight), resorcinol at 3.8%(parts by weight), dibasic ester (DBE) at 7.6%, an acrylate (SR 351HTMPTA) at 56.40% (parts by weight), silane (A187) at 1.2%.

After two minutes from curing at about 31% RH, the three tensilestrength test results of the Example Nine dog bone sample were 199.1,203.8, and 203.0, for an average of 202.0 psi. After two hours fromcuring at about 31% RH, the three tensile strength test results were224.2, 226.6, and 252.8, for an average of 234.5 psi. After 24 hoursfrom curing at about 31% RH, the three tensile strength test resultswere 261.5, 228.5, and 244.2, for an average of 244.7 psi. After 24hours from curing at about 75% RH, the three tensile strength testresults were 129.6, 123.4, and 119.3, for an average of 124.1 psi.

Example Nine

Example Nine utilizes sand (Wedron 520), Part One, and Part Two of thefoundry binder system. Part One (a proprietary mix) includes Bisphenol Fepoxy resin (DER 354) at 68% (parts by weight), Bisphenol A epoxy resin(Dow DER 383) at 2% (parts by weight), and cumene hydroperoxide(TRIGONOX K-90) at 30% (parts by weight). Part Two includes epoxynovolac resin (Dow DEN 431) at 31% (parts by weight), resorcinol at 3.8%(parts by weight), dibasic ester (DBE) at 7.6%, an acrylate (SR 351HTMPTA) at 56.40% (parts by weight), silane (A187) at 1.2%.

After two minutes from curing at about 31% RH, the three tensilestrength test results of the Example Nine dog bone sample were 187.8,200.5, and 195.1, for an average of 194.5 psi. After two hours fromcuring at about 31% RH, the three tensile strength test results were238.1, 242.9, and 227.5, for an average of 236.2 psi. After 24 hoursfrom curing at about 31% RH, the three tensile strength test resultswere 245.2, 221.9, and 250.2, for an average of 239.1 psi. After 24hours from curing at about 75% RH, the three tensile strength testresults were 126.7, 110.1, and 120.1, for an average of 119.0 psi.

Example Ten

Example Ten utilizes sand (Wedron 520), Part One, and Part Two of thefoundry binder system. Part One (a proprietary mix) includes Bisphenol Fepoxy resin (DER 354) at 69% (parts by weight), Bisphenol A epoxy resin(Dow DER 383) at 1% (parts by weight), and cumene hydroperoxide(TRIGONOX K-90) at 30% (parts by weight). Part Two (a proprietary mix)includes epoxy novolac resin (Dow DEN 431) at 36.7% (parts by weight),an acrylate (SR 351H TMPTA) at 62.1% (parts by weight), silane (A187) at1.2%.

After two minutes from curing at about 31% RH, the three tensilestrength test results of the Example Ten dog bone sample were 173.2,185.6, and 193.7, for an average of 184.2 psi. After two hours fromcuring at about 31% RH, the three tensile strength test results were234.2, 238.9, and 243.7, for an average of 238.9 psi. After 24 hoursfrom curing at about 31% RH, the three tensile strength test resultswere 262.6, 232.6, and 233.5, for an average of 242.9 psi. After 24hours from curing at about 75% RH, the three tensile strength testresults were 115.6, 116.8, and 104.9, for an average of 112.4 psi.

Summary of Tensile Strength Examples

The foregoing examples demonstrates that blends of epoxy novolac resinsand bisphenol-F epoxy resin can be used to make cores with adequatetensile strength. Other experiments indicate that the addition ofbisphenol A epoxy resin has does not have a detrimental effect on thetensile strength of the dog bones or foundry cores made with the binder.

Exemplary Shake Out Test

The shake out test for castings has been used extensively to developno-bake and cold box binders with improved shakeout for aluminumcastings in the shakeout test, castings are measured by placing thesolidified casting (specific time from pouring to be determined by testprogram) onto a pneumatic vibrator for a selected time, then the loosesand is removed and the core and retained sand weighed. Cycle isrepeated until 100% of the sand is removed by vibration. A secondarybenefit is the ability to look at surface finish.

A shakeout test was conducted utilizing a core mold made from sand(Badger FW-55), Part One, and Part Two. Part One was formed from PartOne includes Bisphenol F epoxy resin (Dow DER 354) at 70% (parts byweight) and cumene hydroperoxide (TRIGONOX K-90) at 30% (parts byweight). Part Two includes epoxy novolac resin (Dow DEN 431) at 31%(parts by weight), resorcinol at 3.8% (parts by weight), dibasic ester(DBE) at 7.6%, an acrylate (SR 351H TMPTA) at 56.40% (parts by weight),silane (A187) at 1.2%.

Furnace dwell times were measured at six 5-minute intervals (i.e., 5minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, and 30minutes). The furnace temperature was 800° F. The cooling time for eachtest interval was 5 minutes.

For the first shakeout test associated with the 5 minute shakeout testdwell time interval, prior to the dwell time, the weight of thecrucible/pan was 216.83 g, the combined weight of the crucible/pan withthe core sample was 326.05, thus the core sample was 109.22 g. After adwell time of 5 minutes (and cooling for another 5 minutes), thecombined weight of the crucible/pan with the core sample (after burning)was 325.78 g. The difference between the pre-burn combined weight andthe post-burn combined weight was 0.27 (326.05−325.78). The post-burncrucible/pan and burned sand weight was 217.64 g. The burned sand lessthe crucible/pan weight was 0.81 (217.64−216.83). The unburned sandsample weight less the burned sand was 108.41 (109.22−0.81). Thus, theshakeout percentage (% SHAKEOUT) was 0.74% (0.81/109.22×100=0.74%).

For the second shakeout test associated with the 10 minute shakeout testdwell time interval, prior to the dwell time, the weight of thecrucible/pan was 217.19 g, the combined weight of the crucible/pan withthe core sample was 325.72 g, thus the core sample was 108.53 g. After adwell time of 10 minutes (and cooling for another 5 minutes), thecombined weight of the crucible/pan with the core sample (after burning)was 325.26 g. The difference between the pre-burn combined weight andthe post-burn combined weight was 0.46 (325.72−325.26). The post-burncrucible/pan and burned sand weight was 219.26 g. The burned sand lessthe crucible/pan weight was 2.07 (219.26−217.19). The unburned sandsample weight less the burned sand was 106.46 (108.53−2.07). Thus, theshakeout percentage (% SHAKEOUT) was 1.91% (2.07/108.53×100=1.91%).

For the third shakeout test associated with the 15 minute shakeout testdwell time interval, prior to the dwell time, the weight of thecrucible/pan was 215.69 g, the combined weight of the crucible/pan withthe core sample was 324.03, thus the core sample was 108.34 g. After adwell time of 15 minutes (and cooling for another 5 minutes), thecombined weight of the crucible/pan with the core sample (after burning)was 323.19 g. The difference between the pre-burn combined weight andthe post-burn combined weight was 0.84 (324.03−323.19). The post-burncrucible/pan and burned sand weight was 220.21 g. The burned sand lessthe crucible/pan weight was 4.52 (220.21−215.69). The unburned sandsample weight less the burned sand was 103.82 (108.34−4.52). Thus, theshakeout percentage (% SHAKEOUT) was 4.17% (4.52/108.34×100=4.17%).

For the fourth shakeout test associated with the 20 minute shakeout testdwell time interval, prior to the dwell time, the weight of thecrucible/pan was 215.0 g, the combined weight of the crucible/pan withthe core sample was 324.49 g, thus the core sample was 109.49 g. After adwell time of 20 minutes (and cooling for another 5 minutes), thecombined weight of the crucible/pan with the core sample (after burning)was 323.34 g. The difference between the pre-burn combined weight andthe post-burn combined weight was 1.15 (324.49−323.34). The post-burncrucible/pan and burned sand weight was 241.69 g. The burned sand lessthe crucible/pan weight was 26.69 g (241.69−215.0). The unburned sandsample weight less the burned sand was 82.8 g (109.49−26.69). Thus, theshakeout percentage (% SHAKEOUT) was 24.38% (26.69/109.49×100=0.74%).

For the fifth shakeout test associated with the 25 minute shakeout testdwell time interval, prior to the dwell time, the weight of thecrucible/pan was 216.30 g, the combined weight of the crucible/pan withthe core sample was 325.43, thus the core sample was 109.13 g. After adwell time of 25 minutes (and cooling for another 5 minutes), thecombined weight of the crucible/pan with the core sample (after burning)was 324.14 g. The difference between the pre-burn combined weight andthe post-burn combined weight was 1.29 (325.43−24.14). The post-burncrucible/pan and burned sand weight was 282.72 g. The burned sand lessthe crucible/pan weight was 66.44 (282.72−216.30). The unburned sandsample weight less the burned sand was 42.71 (109.13−66.42). Thus, theshakeout percentage (% SHAKEOUT) was 60.86% (66.42/109.13×100=60.86%).

For the sixth shakeout test associated with the 30 minute shakeout testdwell time interval, prior to the dwell time, the weight of thecrucible/pan was 215.31 g, the combined weight of the crucible/pan withthe core sample was 324.92, thus the core sample was 109.61 g. After adwell time of 30 minutes (and cooling for another 5 minutes), thecombined weight of the crucible/pan with the core sample (after burning)was 323.5 g. The difference between the pre-burn combined weight and thepost-burn combined weight was 1.42 (324.92−323.5). The post-burncrucible/pan and burned sand weight was 323.5 g. The burned sand lessthe crucible/pan weight was 109.19 (323.5−215.31). The unburned sandsample weight less the burned sand was 1.42 (109.61−109.19). Thus, theshakeout percentage (% SHAKEOUT) was about 100%(109.19/109.61×100=100%).

Distinctions Over the Prior Art

The foundry binder system of the present disclosure is distinguishedfrom U.S. Pat. No. 6,604,567 inasmuch as no portion of the formulationof the present disclosure (i.e., Part One 102 and Part Two 104; which iscommercially known as HyperSET) includes/utilizes an alkyl silicate asrequired by U.S. Pat. No. 6,604,567. More particularly, the A-187 Silaneof the present disclosure is not an alkyl silicate.

The foundry binder system of the present disclosure is distinguishedfrom U.S. Pat. No. 6,662,854 inasmuch as no portion of the formulationof the present disclosure (i.e., Part One 102 and Part Two 104; which iscommercially known as HyperSET) includes/utilizes an aliphatic epoxyresin as required by U.S. U.S. Pat. No. 6,662,854. More particularly,the bisphenol-F epoxy resin, bisphenol-A epoxy resin, and novolac resinsused in some exemplary formulations discussed above are aromatic resins,not aliphatic resins. As one having ordinary skill in the artrecognizes, aliphatic resins are different from aromatic resins.

The foundry binder system of the present disclosure is distinguishedfrom U.S. Pat. No. 6,684,936 inasmuch as no portion of the formulationof the present disclosure (i.e., Part One 102 and Part Two 104; which iscommercially known as HyperSET) includes/utilizes a benzylic etherphenolic resole resin as required by U.S. Pat. No. 6,684,936. Moreparticularly, the resorcinol and DBE used in some exemplary formulationsdiscussed above are not benzylic ether phenolic resins.

The foundry binder system of the present disclosure (i.e., Part One 102and Part Two 104; which is commercially known as HyperSET) isdistinguished from U.S. Pat. No. 6,686,402 inasmuch some embodiments usebisphenol A epoxy resin that is specifically excluded through Claim 1 ofU.S. Pat. No. 6,686,402.

The foundry binder system of the present disclosure is distinguishedfrom U.S. Pat. No. 7,723,401 inasmuch as no portion of the formulationof the present disclosure (i.e., Part One 102 and Part Two 104; which iscommercially known as HyperSET) includes/utilizes an acrylate 5 to 50parts by weight as required by U.S. Pat. No. 7,723,401. The acrylateused in some exemplary formulations is outside the range provided inU.S. Pat. No. 7,723,401, which causes the foundry binder system of thepresent disclosure to function and react differently and in an improvedmanner. Additionally, U.S. Pat. No. 7,723,401 requires 3 to 6 parts byweight of an organofunctional silane. The A-187 Silane in some exemplaryformulation is outside the range provided in U.S. Pat. No. 7,723,401,which causes the foundry binder system of the present disclosure tofunction and react differently and in an improved manner.

SUNDRY DISCUSSIONS

Also, various inventive concepts may be embodied as one or more methods,of which an example has been provided. The acts performed as part of themethod may be ordered in any suitable way. Accordingly, embodiments maybe constructed in which acts are performed in an order different thanillustrated, which may include performing some acts simultaneously, eventhough shown as sequential acts in illustrative embodiments.

While various inventive embodiments have been described and illustratedherein, those of ordinary skill in the art will readily envision avariety of other means and/or structures for performing the functionand/or obtaining the results and/or one or more of the advantagesdescribed herein, and each of such variations and/or modifications isdeemed to be within the scope of the inventive embodiments describedherein. More generally, those skilled in the art will readily appreciatethat all parameters, dimensions, materials, and configurations describedherein are meant to be exemplary and that the actual parameters,dimensions, materials, and/or configurations will depend upon thespecific application or applications for which the inventive teachingsis/are used. Those skilled in the art will recognize, or be able toascertain using no more than routine experimentation, many equivalentsto the specific inventive embodiments described herein. It is,therefore, to be understood that the foregoing embodiments are presentedby way of example only and that, within the scope of the appended claimsand equivalents thereto, inventive embodiments may be practicedotherwise than as specifically described and claimed. Inventiveembodiments of the present disclosure are directed to each individualfeature, system, article, material, kit, and/or method described herein.In addition, any combination of two or more such features, systems,articles, materials, kits, and/or methods, if such features, systems,articles, materials, kits, and/or methods are not mutually inconsistent,is included within the inventive scope of the present disclosure.

All definitions, as defined and used herein, should be understood tocontrol over dictionary definitions, definitions in documentsincorporated by reference, and/or ordinary meanings of the definedterms.

The indefinite articles “a” and “an,” as used herein in thespecification and in the claims, unless clearly indicated to thecontrary, should be understood to mean “at least one.” The phrase“and/or,” as used herein in the specification and in the claims (if atall), should be understood to mean “either or both” of the elements soconjoined, i.e., elements that are conjunctively present in some casesand disjunctively present in other cases. Multiple elements listed with“and/or” should be construed in the same fashion, i.e., “one or more” ofthe elements so conjoined. Other elements may optionally be presentother than the elements specifically identified by the “and/or” clause,whether related or unrelated to those elements specifically identified.Thus, as a non-limiting example, a reference to “A and/or B”, when usedin conjunction with open-ended language such as “comprising” can refer,in one embodiment, to A only (optionally including elements other thanB); in another embodiment, to B only (optionally including elementsother than A); in yet another embodiment, to both A and B (optionallyincluding other elements); etc. As used herein in the specification andin the claims, “or” should be understood to have the same meaning as“and/or” as defined above. For example, when separating items in a list,“or” or “and/or” shall be interpreted as being inclusive, i.e., theinclusion of at least one, but also including more than one, of a numberor list of elements, and, optionally, additional unlisted items. Onlyterms clearly indicated to the contrary, such as “only one of” or“exactly one of,” or, when used in the claims, “consisting of,” willrefer to the inclusion of exactly one element of a number or list ofelements. In general, the term “or” as used herein shall only beinterpreted as indicating exclusive alternatives (i.e. “one or the otherbut not both”) when preceded by terms of exclusivity, such as “either,”“one of,” “only one of,” or “exactly one of.” “Consisting essentiallyof,” when used in the claims, shall have its ordinary meaning as used inthe field of patent law.

As used herein in the specification and in the claims, the phrase “atleast one,” in reference to a list of one or more elements, should beunderstood to mean at least one element selected from any one or more ofthe elements in the list of elements, but not necessarily including atleast one of each and every element specifically listed within the listof elements and not excluding any combinations of elements in the listof elements. This definition also allows that elements may optionally bepresent other than the elements specifically identified within the listof elements to which the phrase “at least one” refers, whether relatedor unrelated to those elements specifically identified. Thus, as anon-limiting example, “at least one of A and B” (or, equivalently, “atleast one of A or B,” or, equivalently “at least one of A and/or B”) canrefer, in one embodiment, to at least one, optionally including morethan one, A, with no B present (and optionally including elements otherthan B); in another embodiment, to at least one, optionally includingmore than one, B, with no A present (and optionally including elementsother than A); in yet another embodiment, to at least one, optionallyincluding more than one, A, and at least one, optionally including morethan one, B (and optionally including other elements); etc.

In the claims, as well as in the specification above, all transitionalphrases such as “comprising,” “including,” “carrying,” “having,”“containing,” “involving,” “holding,” “composed of,” and the like are tobe understood to be open-ended, i.e., to mean including but not limitedto. Only the transitional phrases “consisting of” and “consistingessentially of” shall be closed or semi-closed transitional phrases,respectively, as set forth in the United States Patent Office Manual ofPatent Examining Procedures.

An embodiment is an implementation or example of the present disclosure.Reference in the specification to “an embodiment,” “one embodiment,”“some embodiments,” “one particular embodiment,” or “other embodiments,”or the like, means that a particular feature, structure, orcharacteristic described in connection with the embodiments is includedin at least some embodiments, but not necessarily all embodiments, ofthe invention. The various appearances “an embodiment,” “oneembodiment,” “some embodiments,” “one particular embodiment,” or “otherembodiments,” or the like, are not necessarily all referring to the sameembodiments.

If this specification states a component, feature, structure, orcharacteristic “may”, “might”, or “could” be included, that particularcomponent, feature, structure, or characteristic is not required to beincluded. If the specification or claim refers to “a” or “an” element,that does not mean there is only one of the element. If thespecification or claims refer to “an additional” element, that does notpreclude there being more than one of the additional element.

Additionally, any method of performing the present disclosure may occurin a sequence different than those described herein. Accordingly, nosequence of the method should be read as a limitation unless explicitlystated. It is recognizable that performing some of the steps of themethod in an different order could achieve a similar result.

In the foregoing description, certain terms have been used for brevity,clearness, and understanding. No unnecessary limitations are to beimplied therefrom beyond the requirement of the prior art because suchterms are used for descriptive purposes and are intended to be broadlyconstrued.

Moreover, the description and illustration of various embodiments of thedisclosure are examples and the disclosure is not limited to the exactdetails shown or described.

What is claimed:
 1. A method of casting a metal article comprising:fabricating a foundry shape by introducing a foundry mix into a patternto form the foundry shape; wherein the foundry mix includes: a firstportion (Part One), wherein Part One includes an epoxy resin in a rangefrom 25 to 70 parts by weight and a free radical initiator; a secondportion (Part Two), wherein Part Two includes an epoxy novolac resin ina range from 10 to 40 parts by weight, a polyhydroxy benezene in a rangefrom 0.5 to 10 parts by weight, an acrylate in a range from 20 to 70parts by weight and a diabasic ester in a range of 2 to 10 parts byweight; provided Part One is not mixed with Part Two prior to orsimultaneous to fabricating the foundry shape the foundry mix, and wheresaid parts by weight are based upon 100 parts of the foundry mix; curingthe shape with gaseous sulfur dioxide; pouring metal while in a liquidstate into the foundry shape; allowing the metal to cool and solidify;and separating the fabricated shape from the pattern.
 2. The method ofclaim 1, wherein the amount of free radical initiator is between 10-40parts by weight.
 3. The method of claim 2, wherein the free radicalinitiator is cumene hydroperoxide.
 4. The method of claim 1, wherein theepoxy resin of Part One is a Bisphenol F epoxy resin.
 5. The method ofclaim 4, wherein Part One further comprises Bisphenol A epoxy resin. 6.The method of claim 5, wherein the Bisphenol A epoxy resin is has aweight of about at least 1 part by weight.
 6. The method of claim 1,wherein the epoxy novolac resin is derived from Bisphenol F epoxy resin.7. The method of claim 1, wherein the polyhydroxy benzene is one ofresorcinol, a non-functionalized resorcinol compound, and afunctionalized resorcinol compound.
 8. The method of claim 1, whereinprior to the fabricating step takes place: providing an aggregate. 9.The method of claim 8, wherein the aggregate is sand.
 10. The method ofclaim 1, wherein Part Two further includes silane in a range from about0.2 to about 5 parts by weight.
 11. The method of claim 1, wherein theresorcinol is in a range from about 1.5 to about 4 parts by weight. 12.A method of casting a metal article comprising: providing a foundryaggregate; fabricating a foundry shape by introducing a foundry mixcomprising an aggregate and a binder system into a pattern to form afoundry shape, wherein the binder system comprises: (1) 10 to 70 partsby weight of an epoxy novolac resin; (2) 0.5 to 10 parts by weight of apolyhydroxy benzene; (3) 20 to 70 parts by weight of a monomeric orpolymeric acrylate; (4) 2 to 10 parts by weight of a dibasic ester; and(5) a free radical initiator; and where said parts by weight are basedupon 100 parts of the foundry mix; mixing parts (1), (2), (3), (4), and(5) within the pattern; curing said shape with gaseous sulfur dioxide;pouring said metal while in a liquid state into said foundry shape;allowing said metal to cool and solidify; and separating the nowfabricated shape from the pattern.
 13. The method of claim 12, whereinpart (2) of the binder system comprises: one of resorcinol, anon-functionalized resorcinol compound, and a functionalized resorcinolcompound.
 14. The method of claim 13, wherein the resorcinol is in arange of about 1.5 to about 4 parts by weight.
 15. The method of claim12, wherein the binder system further comprises: (6) a silane in therange from about 0.2 to about 5 parts by weight.
 16. The method of claim12, wherein the amount of free radical initiator is between 10-40 partsby weight.
 17. The method of claim 15, wherein the free radicalinitiator is cumene hydroperoxide.
 18. The method of claim 12, whereinthe binder system further comprises: (6) an epoxy resin in a range from25 to 70 parts by weight.
 19. The method of claim 18, wherein the epoxyresin of part (6) comprises a Bisphenol F type epoxy resin.
 20. Themethod of claim 19, wherein the epoxy resin further comprises at least 1part by weight of Bisphenol A epoxy resin.